Surface ligand modified silver nanoparticles-based SERS sensing platform for ultrasensitive detection of the pesticide thiram in green tea leaves: roles of coating agents in sensing performance.

Silver nanoparticles (AgNPs) have been regarded as a highly promising substrate for surface-enhanced Raman scattering (SERS) sensors. In this study, we focused on the electrochemical synthesis method by developing three kinds of AgNPs using three different electrolytes: citrate (e-Ag-C), oleic acid (e-Ag-O) and fish mint (Houttuynia cordata Thunb.) extract (e-Ag-bio). The as-prepared AgNPs were characterized and then employed as SERS substrates to detect the pesticide thiram. The obtained results show that e-Ag-O exhibits the best SERS performance. The effect of the coating agent was explained by chemical and electromagnetic enhancements (CM and EM). Although thiram could absorb onto e-Ag-C at the highest level, allowing its Raman signal to be best enhanced via the CM, the smallest interparticle distance of e-Ag-O could have resulted in the largest improvement in the EM. Using e-Ag-O to develop SERS-based sensors for thiram, we obtain the impressive detection limit of 1.04 × 10-10 M in standard samples and 10-9 M in tea leaves. The linear ranges are from 10-4 M to 10-7 M and from 10-7 M to 10-9 M, covering the maximum residue levels for plant commodities established by the United States Environment Protection Agency and European Food Safety Authority (2-13 ppm ∼7.7 × 10-6 M to 5 × 10-5 M).

Revealing the high efficiency of fluorescence quenching of rhodamine B by triangular silver nanodisks due to the inner filter effect mechanism.

Performing effective fluorescence quenching based on a metal nanomaterial is essential to construct fluorescence sensors. Silver nanomaterials are well known as an excellent candidate for an absorber in fluorescence sensing systems. Herein, we investigated the fluorescence quenching of rhodamine B (RhB) in the presence of triangular silver nanodisks in which perfect overlap between the absorption of the absorber and the fluorescence of the fluorophore was observed. The fluorescence quenching mechanism of RhB was investigated under various excitation wavelengths, together with measurement of the fluorescence lifetime. The quenching efficiency of RhB was proportional to the wavelength excitation. Remarkably, the highest efficiency of fluorescence quenching of RhB was achieved (∼60%). The quenching mechanism was investigated and revealed to be mostly due to the inner filter effect (IFE) mechanism, without the contribution of energy transfer. This result shows a completely different story from most previous studies based on silver nanoparticles, where energy transfer was reported to play a significant role.

Developing efficient CuO nanoplate/ZnO nanoparticle hybrid photocatalysts for methylene blue degradation under visible light.

CuO/ZnO nanocomposites with different components can overcome the drawbacks of previously used photocatalysts owing to their promotion in charge separation and transportation, light absorption, and the photo-oxidation of dyes. In this study, CuO nanoplates were synthesized by the hydrothermal method, while ZnO nanoparticles were fabricated by the precipitation method. A series of CuO/ZnO nanocomposites with different ZnO-to-CuO weight ratios, namely, 2 : 8, 4 : 6, 5 : 5, 6 : 4, and 8 : 2 were obtained via a mixing process. X-ray diffraction patterns confirmed the presence of hexagonal wurtzite ZnO and monoclinic CuO in the synthesized CuO/ZnO nanocomposites. Scanning electron microscopy showed the dispersion of ZnO nanoparticles on the surface of CuO nanoplates. Ultraviolet-visible absorption spectra exhibited a slight red-shift in the absorption edge of binary oxides relative to pure ZnO or CuO. All samples were employed for the photocatalytic degradation of methylene blue (MB) under visible light irradiation. The composite samples exhibited enhanced photocatalytic performance compared with pristine CuO or ZnO. This study aimed to examine the effect of the ZnO-to-CuO weight ratio on their photocatalytic performance. The results indicated that among all the synthesized nanocomposites and pristine oxides, the nanocomposite with ZnO and CuO in a proportion of 4 : 6 shows the highest photodegradation activity for the removal of MB with 93% MB photodegraded within 60 min at an initial MB concentration of 5 ppm. The photocatalytic kinetic data were described well by the pseudo-first-order model with a high correlation coefficient of 0.95. The photocatalytic mechanism of the mixed metal oxide was proposed and discussed in detail. The photodegradation characteristic of CuO/ZnO nanostructures is valuable for methylene blue degradation from aqueous solutions as well as environmental purification in various fields.

Enhanced Raman scattering based on a ZnO/Ag nanostructured substrate: an in-depth study of the SERS mechanism.

Combining semiconductor and noble metal nanostructures into a hybrid system has shown many complementary advantages in the optical properties, making them more attractive in practical applications. Herein, we prepared a semiconductor/noble metal hybrid system composed of Ag nanoparticles decorated on ZnO nanoplates acting as a surface-enhanced Raman scattering (SERS) substrate for probing methyl red. The tuning of the optical characteristics of the hybrid system was demonstrated through the changes in the absorption, fluorescence, and Raman spectra. The formation of the local electromagnetic field at the heterostructure interface plays a pivotal role in its SERS activity. Thanks to density functional theory calculations, methyl red's vibrational modes and symmetry properties were assigned to be consistent with the contribution of the neutral trans conformer and protonated state. Then, using Herzberg-Teller-surface selection rules, these assignments strongly support the realization that the SERS mechanism based on the ZnO/Ag substrate has a significant electromagnetic contribution versus the Ag substrate in which charge transfer plays a pivotal role. To the best of our knowledge, this is the first investigation that has clarified the mechanism and advantage of semiconductor/metal (ZnO/Ag nanostructures) even over noble metals (Ag nanoparticles) in SERS applications. Moreover, the SERS behavior based on the ZnO/Ag substrate was also examined and the results indicated high sensitivity and good repeatability.

Synthesis of cuprous oxide/silver (Cu2O/Ag) hybrid as surface-enhanced Raman scattering probe for trace determination of methyl orange.

Recently, there have been publications on preparing hybrid materials between noble metal and semiconductor for applications in surface-enhanced Raman scattering (SERS) substrates to detect some toxic organic dyes. However, the use of cuprous oxide/silver (Cu2O/Ag) to measure the trace amounts of methyl orange (MO) has not been reported. Therefore, in this study, the trace level of MO in water solvent was determined using a SERS substrate based on Cu2O microcubes combined with silver nanoparticles (Ag NPs). Herein, a series of Cu2O/Agx (x= 1-5) hybrids with various Ag amounts was synthesized via a solvothermal method followed by a reduction process, and their SERS performance was studied in detail. X-ray diffraction (XRD) and scanning electron microscopy results confirmed that 10 nm Ag NPs were well dispersed on 200-500 nm Cu2O microcubes to form Cu2O/Ag heterojunctions. Using the as-prepared Cu2O and Cu2O/Agx as MO probe, the Cu2O/Ag5 nanocomposite showed the highest SERS activity of all samples with the limit of detection as low to 1 nM and the enhancement factor as high as 4 × 108. The logarithm of the SERS peak intensity at 1389 cm-1 increased linearly with the logarithm of the concentration of MO in the range from 1 nM to 0.1 mM.

Ag nanoparticles on ZnO nanoplates as a hybrid SERS-active substrate for trace detection of methylene blue.

Decorating two-dimensional (2D) nanomaterials with nanoparticles provides an effective method to integrate their physicochemical properties. In this work, we present the hydrothermal growth process of 2D zinc oxide nanoplates (ZnO NPls), then silver nanoparticles (AgNPs) were uniformly distributed on the surface of ZnO NPls through the reduction procedure of silver nitrate with sodium borohydride to create a metal-semiconductor hybrid. The amount of AgNPs on the ZnO NPls' surface was carefully controlled by varying the volume of silver nitrate (AgNO3) solution. Moreover, the effect of AgNPs on the surface-enhanced Raman scattering (SERS) property of ZnO NPls was thoroughly investigated by using methylene blue (MB) as the target molecule. After calculation, the maximum enhancement factor value for 10-4 M of MB reached 6.2 × 106 for the peak at 1436 cm-1 and the limit of detection was 10-9 M. In addition, the hybrid nanosystem could distinguish MB with good reproducibility over a wide range of concentrations, from 10-9 to 10-4 M. The SERS mechanism is well elucidated based on the chemical and electromagnetic mechanisms related to the synergism of ZnO and Ag in the enhancement of Raman signal. Abundant hot spots located at the gap between adjacent separate Ag nanoparticles and ZnO nanoplates which formed a strong local electromagnetic field and electron transfer between ZnO and Ag are considered to be the key factors affecting the SERS performance of our prepared ZnO/Ag substrates. In this research, we found high sensitivity of ZnO nanoplates/Ag nanoparticles in detecting MB molecules. This unique metal-semiconductor hybrid nanosystem is advantageous for the formation of Raman signals and is thus suitable for the trace detection of methylene blue.

Evaluation of diffusion coefficient of P-glycoprotein molecules labeled with green fluorescent protein in living cell membrane.

The movement of individual molecules inside living cells has recently been resolved by single particles tracking (SPT) method which is a powerful tool for probing the organization and dynamics of the plasma membrane constituents. Effective treatment of metastatic cancers requires the toxic chemotherapy, however this therapy leads to the multidrug resistance phenomenon of the cancer cells, in which the cancer cells resist simultaneously to different drugs with different targets and chemical structures. P-glycoprotein molecules which are responsible for multidrug resistance of many cancer cells have been studied by cancer biologists during past haft of century. Recently, advances in laser and detector technologies have enabled single fluorophores to be visualized in aqueous solution. The development of the total internal reflection fluorescent microscope (TIRFM) provided means to monitor dynamic molecular localization in living cells. In this paper, P-glycoproteins (PGP) were labeled with green fluorescent protein (GFP) in living cell membrane of Madin-Darby canine kidney (MDCK) and the TIRFM method was used to characterize the dynamics of individual protein molecules on the surface of living cells. An evanescent field was produced by a totally internally reflected and a laser beam was illuminated the glass-water interface. GFP-PGP proteins that entered the evanescent field appeared as individual spots of light which were slighter than background fluorescence. We obtained high-resolution images and diffusion maps of membrane proteins on cell surface and showed the local diffusion properties of specific proteins on single cells. We also determined the diffusion coefficient, the mean square displacement and the average velocity of the tracked particles, as well as the heterogeneity of the cell environment. This study enabled us to understand single-molecule features in living cell and measure the diffusion kinetics of membrane-bound molecules.

Tunable LSPR of silver/gold bimetallic nanoframes and their SERS activity for methyl red detection.

Ag/Au bimetallic nanostructures have received much attention in surface-enhanced Raman scattering (SERS). However, the synthesis of this nanostructure type still remains a challenge. In the present research, Ag/Au nanoframes were synthesized via a simple room temperature solution phase chemical reduction method using pre-synthesized triangular Ag nanoplates as templates in the presence of appropriate amounts of HAuCl4. Controlling experimental parameters was applied for understanding of the growth mechanism. The galvanic exchange reaction resulted in a uniform deposition of the Au shell on the Ag nanoplates and the Ag core was removed which generated triangular hollow nanoframes. It is found that the amount of HAuCl4 added to the growth solution played a key role in controlling the Ag/Au nanoframes. The resultant silver/gold nanoframes with average size of 50 nm were applied in detecting methyl red (MR) in the solution-phase using an excitation wavelength laser of 532 nm. The SERS signal was greatly enhanced owing to the tunable plasmonic peaks in the visible region (400-650 nm). The limit of detection (LOD) of MR in diluted solution was 10-6 M. The enhancement factor (EF) was about 8 × 104 toward 10-5 M of MR. Interestingly, the linear dependence between the logarithm of the SERS signal intensity (log I) and the logarithm of the MR concentration (log C) occurred in the range from 10-6 to 10-4 M. Our work promises the application of Ag/Au nanoframes as a chemical sensor in detecting MR molecules at low concentration with high performance.

Facile synthesis of silver/gold alloy nanoparticles for ultra-sensitive rhodamine B detection.

The synthesis of Ag/Au nanoparticles (NPs) in a controlled manner has been a challenge for a long time. The aim of this report is to present a systematic study on the fabrication, characterization of Ag/Au alloy NP-based surface-enhanced Raman spectroscopy (SERS) substrates. Silver (Ag) and gold (Au) colloidal NPs were prepared by chemical reduction route of the corresponding metal salts by trisodium citrate (TSC). Ag/Au alloy nanoparticles with varying molar fractions are prepared in aqueous solution by the simultaneous reduction of AgNO3 and HAuCl4 by TSC. The composition of Ag and Au in the alloy samples was controlled by tuning the molar ratio of Ag+/Au3+ in the mixture solution. The morphologies of the different products were characterized by TEM, and the size of obtained samples was in the range of 40 to 60 nm. The resulting samples were denoted as AgNPs, AuNPs, Ag3Au, AgAu, and AgAu3 NPs. In order to compare the optical property of the Ag/Au alloy and Ag/Au mixture, we mixed the pure Ag and Au NPs with different ratios to obtain the aggregated nanoparticles. Ag/Au alloy NPs were demonstrated as an ultrasensitive SERS substrate for the detection of rhodamine B (RhB) molecules. The concentration of RhB ranged from 10-11 to 10-5 M. The effect of the Au content on the optical and SERS properties of the Ag/Au alloys was studied. The obtained results show that the Au content in the Ag/Au alloys play an important role in the physical properties of Ag/Au alloy NPs. The SERS spectra of RhB from the as-prepared Ag/Au alloy NP substrates indicated the superior enhancement with high reproducibility and sensitivity compared to those of Ag or Au samples. Interestingly, the highest SERS activity was achieved for the Ag3Au sample with an enhancement factor larger than 1010 for 10-11 M RhB and a limit of detection (LOD) at 10-11 M, as well as good long-term stability after storage for 1 year. As far as we know, this is the highest sensitivity record of RhB by SERS detection. Furthermore, the composition-dependent SERS activity was explained in detail. These advantages demonstrated the potential for growing Ag/Au alloy NP-based SERS substrates in food safety and bioanalysis.

Phosphate Adsorption by Silver Nanoparticles-Loaded Activated Carbon derived from Tea Residue.

This study presents the removal of phosphate from aqueous solution using a new silver nanoparticles-loaded tea activated carbon (AgNPs-TAC) material. In order to reduce costs, the tea activated carbon was produced from tea residue. Batch adsorption experiments were conducted to evaluate the effects of impregnation ratio of AgNPs and TAC, pH solution, contact time, initial phosphate concentration and dose of AgNPs-AC on removing phosphate from aqueous solution. Results show that the best conditions for phosphate adsorption occurred at the impregnation ratio AgNPs/TAC of 3% w/w, pH 3, and contact time lasting 150 min. The maximum adsorption capacity of phosphate on AgNPs-TAC determined by the Langmuir model was 13.62 mg/g at an initial phosphate concentration of 30 mg/L. The adsorption isotherm of phosphate on AgNPs-TAC fits well with both the Langmuir and Sips models. The adsorption kinetics data were also described well by the pseudo-first-order and pseudo-second-order models with high correlation coefficients of 0.978 and 0.966, respectively. The adsorption process was controlled by chemisorption through complexes and ligand exchange mechanisms. This study suggests that AgNPs-TAC is a promising, low cost adsorbent for phosphate removal from aqueous solution.

The structural transition of bimetallic Ag-Au from core/shell to alloy and SERS application.

It is well-known that Ag-Au bimetallic nanoplates have attracted significant research interest due to their unique plasmonic properties and surface-enhanced Raman scattering (SERS). In recent years, there have been many studies on the fabrication of bimetallic nanostructures. However, controlling the shape, size, and structure of bimetallic nanostructures still has many challenges. In this work, we present the results of the synthesis of silver nanoplates (Ag NPls), and Ag-Au bimetallic core/shell and alloy nanostructures, using seed-mediated growth under green LED excitation and a gold salt (HAuCl4) as a precursor of gold. The results show that the optical properties and crystal structure strongly depend on the amount of added gold salt. Interestingly, when the amount of gold(x) in the sample was less than 0.6 µmol (x < 0.6 µmol), the structural nature of Ag-Au was core/shell, in contrast x > 0.6 µmol gave the alloy structure. The morphology of the obtained nanostructures was investigated using the field emission scanning electron microscopy (FESEM) technique. The UV-Vis extinction spectra of Ag-Au nanostructures showed localized surface plasmon resonance (LSPR) bands in the spectral range of 402-627 nm which changed from two peaks to one peak as the amount of gold increased. Ag-Au core/shell and alloy nanostructures were utilized as surface enhanced Raman scattering (SERS) substrates to detect methylene blue (MB) (10-7 M concentration). Our experimental observations indicated that the highest enhancement factor (EF) of about 1.2 × 107 was obtained with Ag-Au alloy. Our detailed investigations revealed that the Ag-Au alloy exhibited significant EF compared to pure metal Ag and Ag-Au core/shell nanostructures. Moreover, the analysis of the data revealed a linear dependence between the logarithm of concentration (log C) and the logarithm of SERS signal intensity (log I) in the range of 10-7-10-4 M with a correlation coefficient (R 2) of 0.994. This research helps us understand better the SERS mechanism and the application of Raman spectroscopy on a bimetallic surface.

The sensitive detection of methylene blue using silver nanodecahedra prepared through a photochemical route.

In this work, we have carried out systematic studies on the critical role of polyvinyl pyrrolidone (PVP) and citrate in the well-known chemical reduction route to synthesize silver nanodecahedra (AgND). Silver nitrate (AgNO3) was used as silver source, which can be directly converted to metallic silver after being reduced by sodium borohydride (NaBH4) under blue light-emitting diode (LED) irradiation (λ max = 465 nm), and polyvinyl pyrrolidone (PVP) as a capping agent to assist the growth of AgND. The obtained products were silver nanodecahedra of excellent uniformity and stability with high efficiency and yield. The results showed that PVP acted as a capping agent to stabilize the silver nanoparticles, prolonging the initiation time required for nanodecahedra nucleation, thus inducing anisotropic growth, allowing the size and morphology of the AgND to be controlled successfully. This improved understanding allows a consistent process for the synthesis of AgND with significantly enhanced reproducibility to be developed and the formation mechanism of these nanostructures to be elucidated. This is a simple, cost-effective and easily reproducible method for creating AgND. The typical absorption maxima in the UV-vis spectroscopy of Ag seeds was λ max ∼400 nm and that of AgND was λ max ∼480 nm. The size of the prepared AgND was in the range of 60-80 nm. SEM images confirmed the uniform and high density of AgND when the concentration of PVP was 0.5 mM. The XRD pattern showed that the final product of AgND was highly crystallized. In addition, the prepared AgND can be used to detect methylene blue (MB) in a sensitive manner with good reproducibility and stability using Surface-Enhanced Raman Scattering (SERS) phenomenon. Out of the obtained products, the AgND prepared with 50 min blue LED light irradiation (AgND-50) displayed the strongest SERS signal. Interestingly, MB in diluted solution can be detected with a concentration as low as 10-7 M (the limit of detection, LOD) and the linear dependence between SERS intensity and the MB concentration occurred in the range from 10-7 to 10-6 M. The enhancement factor (EF) of the SERS effect was about 1.602 × 106 with a MB concentration of 10-7 M using 532 nm laser excitation.

Gold nanocrescents for remotely measuring and controlling local temperature.

We present a novel technique to remotely measure and control the local temperature within a medium. This technique is based on the observation of the rotational Brownian motion of gold nanocrescent particles, which possess a strong anisotropic light interaction due to their plasmonic properties. Rotational scattering correlation spectroscopy performed on a single nanoparticle is able to determine the local temperature with high accuracy. These nano-thermometers can simultaneously play the role of nano-heaters when absorbing the light of a focused laser beam.